Imidoylketene-alpha-oxoketenimine and alpha-oxoketene-alpha-oxoketene rearrangements. 1,3-Shifts of substituted phenyl groups

1,3-Phenyl shifts interconvert imidoylketenes 1 and alpha-oxoketenimines 2 and, likewise, alpha-oxoketenes 3 automerize by this 1,3-shift. These rearrangements usually take place in the gas phase under conditions of. ash vacuum thermolysis. Energy profiles calculated at the B3LYP/6-31G(d, p) and B3LYP/6311 + G(3df,2p)//B3LYP/6-31G(d,p) levels demonstrate that electron donating substituents ( D) in the migrating phenyl group and electron withdrawing ones ( W) in the non-migrating phenyl group, can stabilise the transition states TS1 and TS2 to the extent that activation barriers of ca. 100 kJ mol(-1) or less are obtained; i.e. enough to make these reactions potentially observable in solution at ordinary temperatures. The calculated transition state energies Delta G(TS1) show an excellent correlation with the Hammett constants sigma(p)(W) and sigma(p) +(D).

The Las Campanas/Anglo-Australian Telescope Rich Cluster Survey - III. Spectroscopic studies of X-ray bright galaxy clusters at z similar to 0.1

We present the analysis of the spectroscopic and photometric catalogues of 11 X-ray luminous clusters at 0.07 < z < 0.16 from the Las Campanas/Anglo-Australian Telescope Rich Cluster Survey. Our spectroscopic data set consists of over 1600 galaxy cluster members, of which two-thirds are outside r(200). These spectra allow us to assign cluster membership using a detailed mass model and expand on our previous work on the cluster colour-magnitude relation ( CMR) where membership was inferred statistically. We confirm that the modal colours of galaxies on the CMR become progressively bluer with increasing radius d( B - R)/dr(p) = - 0.011 +/- 0.003 and with decreasing local galaxy density d( B - R)/dlog ( Sigma)= - 0.062 +/- 0.009. Interpreted as an age effect, we hypothesize that these trends in galaxy colour should be reflected in mean H delta equivalent width. We confirm that passive galaxies in the cluster increase in Hd line strength as dH delta/dr(p) = 0.35 +/- 0.06. Therefore, those galaxies in the cluster outskirts may have younger luminosity-weighted stellar populations; up to 3 Gyr younger than those in the cluster centre assuming d( B - R)/dt = 0.03 mag per Gyr. A variation of star formation rate, as measured by [ O II]lambda 3727 angstrom, with increasing local density of the environment is discernible and is shown to be in broad agreement with previous studies from the 2dF Galaxy Redshift Survey and the Sloan Digital Sky Survey. We divide our spectra into a variety of types based upon the MORPHs classification scheme. We find that clusters at z similar to 0.1 are less active than their higher-redshift analogues: about 60 per cent of the cluster galaxy population is non-star forming, with a further 20 per cent in the post-starburst class and 20 per cent in the currently active class, demonstrating that evolution is visible within the past 2 - 3 Gyr. We also investigate unusual populations of blue and very red non-star forming galaxies and we suggest that the former are likely to be the progenitors of galaxies which will lie on the CMR, while the colours of the latter possibly reflect dust reddening. We show that the cluster galaxies at large radii consist of both backsplash ones and those that are infalling to the cluster for the first time. We make a comparison to the field population at z similar to 0.1 and examine the broad differences between the two populations. Individually, the clusters show significant variation in their galaxy populations which we suggest reflects their recent infall histories.

Excitation spectra of the spin-1/2 triangular-lattice Heisenberg antiferromagnet

We use series expansion methods to calculate the dispersion relation of the one-magnon excitations for the spin-(1)/(2) triangular-lattice nearest-neighbor Heisenberg antiferromagnet above a three-sublattice ordered ground state. Several striking features are observed compared to the classical (large-S) spin-wave spectra. Whereas, at low energies the dispersion is only weakly renormalized by quantum fluctuations, significant anomalies are observed at high energies. In particular, we find rotonlike minima at special wave vectors and strong downward renormalization in large parts of the Brillouin zone, leading to very flat or dispersionless modes. We present detailed comparison of our calculated excitation energies in the Brillouin zone with the spin-wave dispersion to order 1/S calculated recently by Starykh, Chubukov, and Abanov [Phys. Rev. B74, 180403(R) (2006)]. We find many common features but also some quantitative and qualitative differences. We show that at temperatures as low as 0.1J the thermally excited rotons make a significant contribution to the entropy. Consequently, unlike for the square lattice model, a nonlinear sigma model description of the finite-temperature properties is only applicable at temperatures < 0.1J. Finally, we review recent NMR measurements on the organic compound kappa-(BEDT-TTF)(2)Cu-2(CN)(3). We argue that these are inconsistent with long-range order and a description of the low-energy excitations in terms of interacting magnons, and that therefore a Heisenberg model with only nearest-neighbor exchange does not offer an adequate description of this material.